KR101492652B1 - Antimicrobial agent - Google Patents

Abstract

The present invention relates to the use of an inorganic material which produces hydrogen cations in contact with an aqueous medium, said hydrogen cations giving rise to an antibacterial effect, said material comprising molybdenum and / or tungsten.

Description

ANTIMICROBIAL AGENT

The present invention relates to the use of a substance to obtain an antibacterial effect.

Microorganisms such as bacteria and fungi are ubiquitous in our living space and exist on a wide variety of surfaces. Many microorganisms are pathogens, and their spread and / or control thus play a special role in public health and hygiene. If these microorganisms enter our bodies, they can cause life-threatening infections. If a hospital gets this infection, it is called a hospital infection.

It begins with the assumption that in the world every two years, in double digits, a billion Euros is required to eliminate the damage caused by the hospital infection. Thus, the control of pathogenic microorganisms plays a special role in public health and hygiene.

In addition to preventing and / or killing undesirable microorganisms as antibiotics, for example, as a precautionary measure, it is becoming increasingly important to create a space that is detrimental to the survival of microorganisms. Among these preventive measures, the use of silver as an additive in organic and inorganic materials has become increasingly important over the last few years. Here, silver ions hinder the important function of microorganisms. Nowadays, silver ions are being carried on the assumption that they block enzymes in cells and prevent their essential transport functions. But also the impairment of the structural strength of the cell and / or the damage of the membrane structure with an additional effect. These effects can lead to cell damage and / or cell death. In addition, silver has a very broad activity range for multi-resistant bacteria. It is sufficient to achieve a long-term effect at low doses. This is called a minor action effect. Organic compounds are still added in some cases to increase the effect of silver. The presence of sufficient silver ions is always important. Therefore, a nano-sized silver powder called so-called silver nano is used to form a large particle surface.

Silver has no toxic side effects in a wide dosage range. Only if silver is accumulated too much in the body can lead to addiction, irreversible skin and gray discoloration of mucous membranes. In addition, an increase in silver concentration may cause taste disorders, olfactory disorders, and cerebral convulsions.

Furthermore, it should be noted that, in general, the interaction between nanoscale particles and the human body has not yet been sufficiently investigated. Extensive research plans have only recently begun. The antimicrobial effect of silver is not sufficient for various applications. The effect is given up to 0.25 moles of physiological saline. Beyond this, silver chloride is produced. The inevitable disadvantage of using silver nano is in an unsatisfactory cost situation. On the one hand, this is due to the high price of silver, and on the other hand the processing of silver into nanoparticles is time-consuming and expensive. The problem is further with the silver nano process, which is due to the formation of agglomerations and clusters. For this reason, the active surface is reduced and the antibacterial effect is also reduced as an additional result. To prevent this, silver nano deposits on the surface of a carrier, for example TiO ₂ , which in turn increases production costs.

Thus, attempts have been made to discover the antimicrobial, microbicidal and germicidal effects of other metals. For example, copper also has a strong antimicrobial effect, but it is too toxic. So far, these effects have been found in the following metals in decreasing order of their effectiveness: as a result of search terms as a minor action in the Internet Wikipedia: mercury, silver, copper, tin, iron, lead and bismuth . Two inert and expensive metals, gold and osmium, also have this effect.

However, in many applications, besides the sufficient antimicrobial effect, the active substance is required to be generally biocompatible without any cytotoxic and clotting properties. Active substances such as mercury, bismuth or copper do not have these properties due to their high cytotoxicity and uncommitted biocompatibility.

Numerous patents and non-patent documents deal with the manufacture and use of silver nano. Additional metals and inorganic compounds are listed in specific cases only. US 5,520,664 describes a catheter made of plastic. The atoms are introduced by ion implantation to obtain an antimicrobial effect. Silver, chromium, aluminum, nickel, tungsten, molybdenum, platinum, iridium, gold, silver, mercury, copper, zinc and cadmium are referred to as metals having an antibacterial effect. However, only silver and copper are mentioned as embodiments and specific embodiments.

JP 2001-54320 describes a plastic material comprising a mixture of 0.005 to 1% by weight of molybdenum trioxide and silver oxide. The present invention relates to an antibacterial resin component and a film which can be used as a partition material of a clean room and which can be used in the top layer of flooring, lining, briefcase, desk rug, tablecloth, The problem here is that when an inorganic, antibacterial active material is contained, the transparency of a plastic material such as a vinyl chloride resin is lost. The loss of transparency is prevented by the incorporation of hexavalent molybdenum oxide. This application easily reveals that if the weight ratio of molybdenum trioxide to silver oxide exceeds 95: 5, the antimicrobial effect can no longer be obtained. Therefore, the antimicrobial effect is not attributable to the molybdenum oxide itself. When the ratio of molybdenum oxide to silver oxide is less than 30: 70, that is, when the molybdenum oxide fraction is small, discoloration of the vinyl chloride resin occurs.

JP 2001-04022 discloses an antibacterial plastic material containing both an organic component and a metal component having an antibacterial effect. Silver, platinum, copper, zinc, nickel, cobalt, molybdenum and chromium are referred to as metal components having an antibacterial effect. However, silver and copper are again mentioned as active only in the embodiment and the preferred embodiment.

JP 2000-143369 discloses a glaze for a ceramic component containing molybdic acid silver. Here, 0.01 to 1% of molybdic acid is converted to metallic silver by adding silver. The effect is increased by the addition of 10 to 50% titanium oxide.

The antimicrobial effect can also be obtained by a component having a photooxidizing effect. For this reason, reactive free radicals are formed which damage microorganisms. JP 11012479 discloses antibacterial plastic materials comprising organic and inorganic components. Additional compounds such as silver, metal particles such as zinc and copper and additional compounds such as calcium zinc phosphate, ceramic, glass powder, aluminum silicate, titanium zeolite, apatite and calcium carbonate are mentioned as examples of inorganic components. Here, metal oxides such as zinc oxide, titanium oxide or molybdenum oxide act as a catalyst for the photo-oxidation effect. As a result, JP 11012479 discloses that the antimicrobial effect occurs only when the photo-oxidation mechanism occurs, that is, the precondition of the effect is the generation of electromagnetic radiation.

The availability of inexpensive materials with antibacterial effects is becoming increasingly important. This characteristic is particularly important in places where a lot of people are crowded or where hygiene is very demanding, such as in hospitals, medical practices, nursing homes and public institutions. Here, it is particularly important to reduce intranasal infection. It is estimated that infection can occur in 0.5% of all hip implants and 2 to 4% of all knee implants. There is a particularly high risk of infection in catheters. In addition, there is also a need to control and / or prevent the wetting and propagation of microorganisms in more applications.

In addition to the availability of materials with antimicrobial activity, it is also important that the effectiveness of the antimicrobial active material is not compromised even if it is included in a composite material made from the article, such as catheter implants, filters, tubes, containers,

In principle, the production of plastic materials is inexpensive and their handling is simple. They are therefore particularly preferred in many applications. However, there is a problem that different kinds of plastic materials must be used for other applications because the properties such as flexibility and / or rigidity and working stress depend on the kind of plastic material. Not all plastic materials are suitable for all applications, for example catheters or infusion bags should still have certain flexibility in contrast to implants or waste containers. Therefore, the type of each plastic material used should be tested as to how the antimicrobial material should be used properly with the plastic material to combine with the plastic material to maintain their effectiveness and / or to obtain their effect. However, this results in a series of time-consuming, expensive and extensive tests, that is, for each preferred application, this time leads to higher production costs.

Accordingly, an object of the present invention is to provide an active material having a higher antibacterial effect than silver nano. The active substance forms only a few cytotoxic and clotting and also has high general biocompatibility for medical applications. In addition, the active material has a high cost-benefit ratio and advantageous process characteristics. Further, if the material has an antibacterial effect in the form of nano-sized particles (particle size of less than 100 nm), as well as in the form of non-inhalable particles (particle size of 500 nm or more) and / Do. It is also desirable that a composite material comprising an antimicrobial active material and having many uses can be made such that the material retains its full effect in the composite material.

This combined purpose is achieved by using an inorganic material which causes the formation of hydrogen cations upon contact with a water-soluble medium to obtain an antimicrobial effect, characterized in that the material comprises molybdenum and / or tungsten.

The generation of hydrogen cations which lower the pH value of the medium upon contact with the substance, while the micro-action effect, i.e. the damage effect of metal cations on living cells, has been used to date to the inorganic active materials, It is a point. Here, the free protons themselves attach themselves to the water molecules that form oxonium ions (H ₃ O ⁺ ) because of their very small radius. If the concentration ratio allows this, binding of oxonium ions to some water molecules can occur. Thus, besides H ⁺ , the cations produced by the reaction of water with H ⁺ and their hydrates are also designated as hydrogen cations. In addition to oxonium ions (H ₃ O ⁺ ), there are Zundel cations (H ₅ O ₂ ⁺ ) and Eigen cations (H ₉ O ₄ ⁺ ).

The molybdenum oxide reacts with, for example, water and forms molybdic acid (H ₂ MoO ₄ ), which in turn reacts with water to form H ₃ O ⁺ and MoO ₄ ^- or MoO ₄ ^{2 -} . Tungsten oxide also produces water and tungstic acid (H ₂ WO ₄ ), which reacts with water to produce H ₃ O ⁺ and WO ₄ ^- or WO ₄ ^{2 -} . According to Arrhenius, hydrogen cations are carriers of acidic properties. The pH value is the negative decimal logarithm of the hydrogen ion concentration value in mole / liter. For a pure neutral solution of water, the hydrogen and OH ^- (hydroxide) ions have the same value (10 ^-7 mole / l) and the pH value is 7. If the material forms a hydrogen cation upon contact with a water-soluble medium, the value of the hydrogen cation increases, and thus the aqueous medium becomes acidic.

Surprisingly, it has been found that a material which produces hydrogen cations upon contact with a water-soluble medium has an excellent antimicrobial effect. The fundamental advantage lies in the fact that the material is not substantially consumed. This is especially true when the material has low solubility in the aqueous medium. The solubility is preferably less than 0.1 mole / l. The solubility of the molybdenum oxide and tungsten oxide is less than 0.02 mole / l. Thus, the antimicrobial effect is present in almost no time limit.

The aqueous medium may be, for example, water, solution or suspension. An example of a solution is a body fluid, and an example of a suspension is a liquid tissue. Here, it is sufficient that the water-soluble medium exists on the surface of the substance in the form of a thin layer. As with the case of adsorbates, the effects of the present invention have already been achieved with film thicknesses in the nanometer range. Therefore, the effect of the present invention already occurs when the material is exposed to air. Due to the formation of hydrogen cations, the pH value is typically lower than 6, preferably lower than 5. The resulting acid environment causes microbial death.

The effect of the substances according to the invention has been investigated by a series of extensively designed tests. Here, antibacterial effects and, in part, cytotoxicity and clotting properties were also tested. As described in the examples of molybdenum- or tungsten-containing materials, surfaces whose surfaces are present in oxidized or oxidized form are particularly effective. Molybdenum can exist in various oxidation forms (VI, V, IV) and participates in the redox process to form relatively weak complexes with physiologically important compounds. Although molybdenum occupies an essential biochemical moiety, it does not bind to physiologically important compounds to a degree that is sufficiently strong to have a severe disruptive effect on the metabolic process. Therefore, there is no toxicity to human body. Molybdenum should be ingested in animals and plants and transported in the form of simple molybdate ions [MoO ₄ ] ^{2 -} . This [MoO ₄ ] ^2- anion can pass through the cell membrane without damage to the cell. Therefore, molybdenum should be carried on the assumption that it is not cytotoxic. The coagulation effect is also unknown. Thus, molybdenum is also suitable for medical applications. Tungsten-containing materials also have a high antimicrobial effect. Currently, there is some clotting effect in the first test, so there is no definite explanation for clotting. Whether this is a tungsten intrinsic property or whether it depends on the processing conditions should still be apparent.

In addition to molybdenum- and tungsten-containing materials, antimicrobial effects associated with lowering pH values have also been found in niobium oxide, manganese oxide, and silicon carbide.

In order to specify the antimicrobial effect, the method described in detail in the following professional paper was used.

Fremdkorper-assoziierte Infektionen in der Intensivmedizin - Therapie und Pravention, J. P. Guggenbichler, Antibiotika Monitor 20 (3), 2004, pages 52 to 64

Inzidenz und Pravention Fremdkorper-assoziierter Infektionen, J. P. Guggenbichler, Biomaterialien 5 (4) 2004, pages 228-236.

In particular, the roll-out incubation method described above has proved its utility for testing the antimicrobial effect. Here, a sample of the active substance is injected into the bacterial suspension for a certain period of time, for example 3 hours. Germs grow on the surface. After this time, the sample is rolled across the so-called baby agar medium and placed in sterile saline. This process is repeated several times every three hours. These three-hourly repeated roll-out activities provide information on whether a bacterial-depleting or bacterial-killing effect occurs, and if so, and the extent of its effect. This method can be used to test other microorganisms, bacteria and viruses. Tests to demonstrate the effect of the substances according to the invention were carried out separately on the standard strains Pseudomonas aeruginosa, E. coli, and Staphylococcus aureus. Silver and copper were used as reference materials.

As already mentioned, it was possible to obtain the best results with materials containing molybdenum and tungsten. Here, it is essential for the present invention that molybdenum oxide or tungsten oxide is formed at the boundary portion between the molybdenum- or tungsten-base active material. If the formation of these oxides does not occur to a sufficient extent or the corresponding form, there is no antimicrobial effect. This also explains why molybdenum and tungsten have not yet been used as antimicrobial active materials.

The antimicrobial effect can advantageously be adjusted by thermal pre-oxidation at a temperature of 300 DEG C or higher. Pre-oxidation can also be performed chemically or electrochemically. This pre-oxidation is necessary in the case of solid Mo and W samples. It has now been found that, compared to an oxide film formed with in situ, the pre-oxidized material by annealing has a better antimicrobial effect. Pre-oxidation should be carried out especially when the conditions used do not cause any sufficient oxidation. It is also important here that the oxide film has a large specific surface.

In addition to pure molybdenum and pure tungsten, compounds that are sufficiently stable and form an oxide film on their surface and alloys of these compounds are also effective. Molybdenum compounds having an antibacterial effect include molybdenum carbide, molybdenum nitride, molybdenum silicide and molybdenum sulfide. Molybdenum, molybdenum oxides and the above-mentioned materials are also commercially available in very fine form with particle sizes according to Fisher less than 1 [mu] m. Among the suitable molybdenum alloys, an alloy of molybdenum and 0.1 to 1 wt% of La ₂ O ₃ , molybdenum and 0.5 wt% of Ti, 0.08 wt% of Zr, 0.01 to 0.04 wt% of C, molybdenum and 5 to 50 An alloy of Re with% by weight, an alloy of molybdenum with 1.2% by weight of Hf and 0.02 to 0.15% by weight of C should be mentioned.

These alloys form an antimicrobial active oxide film on the surface. In the case of tungsten, tungsten materials are also effective in forming oxide films by in situ or preceding annealing. In addition to pure oxidized tungsten, oxides of tungsten are also effective. Here, tungsten blue oxide (WO _{2 , 84} ) and WO ₃ are specifically mentioned. Tungsten alloy, 0.1 to 1 wt.% Of La ₂ O ₃ , tungsten and 1 to 26 wt.% Of Re alloy also have a good antimicrobial effect. Tungsten carbide, tungsten silicide, and tungsten sulfide are particularly suitable among the tungsten compounds capable of forming an oxide film on the surface.

 If silver is present in a very fine particle state, the antimicrobial effect occurs only to a sufficient extent in silver, while the material according to the invention also has an antimicrobial effect if they are present in dense, dense form. Tests show that the effect is still increased when the surface expands. Therefore, it can be advantageous for many applications if the material is in the form of a porous material.

It is also effective when the material is present as a layer or a component of a layer. The layer of molybdenum oxide and the layer of tungsten oxide and / or also the molybdenum layer and the tungsten layer are oxidized by in-situ oxidation or by in-situ oxidation if in situ oxidation is not occurring sufficiently, which proved to be particularly advantageous. The layer may be deposited on a plastic material, ceramic or metal. Particularly suitable deposition processes are thermal deposition, sputtering, chemical vapor deposition, electrodeposition, and electric arc deposition. The molybdenum oxide layer can be produced by a chemical vapor deposition method, for example, by decomposition of molybdenum hexacarbonyl (Mo (CO) ₆ ) at atmospheric pressure. Organometallic CVD (MOCVD) is also possible. Here, molybdenum acetylacetonate (MoO ₂ (CH ₃ COCH ₂ COCH ₂ ) ₂ ) can be used, for example, as an organometallic compound. Molybdenum oxide films can be produced using these organometallic compounds in the temperature range of approximately 400 to 500 ° C, and Mo ₉ O ₂₆ and Mo ₄ O ₁₁ can be detected in addition to MoO ₃ . Particle sizes smaller than 1 μm with a layer thickness in the range of a few μm promote the antimicrobial effect. Molybdenum oxide and tungsten oxide films can also be deposited by reactive electron-beam evaporation. Such a film also has a very fine-particle structure with pores sized from 50 to 100 nm.

Electrophoresis and sol-gel processes should still be mentioned as particularly suitable deposition methods.

If the layer is deposited on a metal, common implant materials such as titanium, iron and cobalt, and alloys thereof are preferred. Further, in the case of the ceramic substrate material, it is preferable to proceed from an established material such as ZrO ₂ and Al ₂ O ₃ having a purity higher than 99 wt%. The layer may also be deposited on a glass or glass ceramic.

As already mentioned, the effect increases if the material has as wide a surface as possible for the water-soluble medium. In particular, good results can be obtained if the layer has a sponge porous structure with pores of 50 to 900 탆 in size. Such a porous structure can be prepared, for example, by depositing an antimicrobially active substance from a gas phase in slurry form or an optional subsequent annealing treatment. Also, if the layer is in the form of an island, in the form of a substantially unconnected mass, it can have a large surface. It is particularly advantageous when such island-like masses cover 40 to 90% of the surface of the substrate material. The size of each mass of material is preferably less than 5 mu m. If the material according to the invention is used in powder form, it will suffice for many applications. Thus, if very fine-particle type powders are used, that is to say that the particle size according to the fisher is less than 5 mu m, advantageously less than 1 mu m is advantageous.

The best results can be obtained through metal composite and / or composite powders. Here, the composite material may also be present in the form of a composite powder. Such a metal composite material further includes a chemically inert metal in addition to the material according to the present invention. Here, the interaction between the chemically inert metal promotes the formation of hydrogen cations. A mixture of the materials according to the invention and the inert metal has an antimicrobial effect even if the sample is not pre-oxidized.

Here, the chemically inactive metal is preferably silver, copper, tin, or an alloy thereof. Molybdenum-silver, molybdenum-copper, molybdenum-tin, tungsten-silver, tungsten-copper and tungsten-tin, which are metal composites, are particularly advantageous. Here, the content of molybdenum and / or tungsten is preferably 10 to 90 atomic%, and when 30 to 80 atomic%, the best results can be obtained.

Unless the material has cytotoxicity and clotting properties, the use of silver is advantageous. However, these characteristics do not play any role in many applications. Here, sanitary service components are mentioned by way of example. Here copper can be used in place of expensive silver, which exceeds silver in its antimicrobial effect. If molybdenum-copper or tungsten-copper powder is added to other materials, very high effects are also obtained. Further, the metal composite material may also be present in a layer or in a compact form, for example as a porous shaped body. Manufacturing can be advantageously performed by penetration techniques for dense composites.

In addition, the materials according to the invention can be used for the production of antibacterial plastic materials.

Here, a composite material comprising a material according to the present invention is particularly advantageous if such a composite material comprises one or more materials, and at least one of the materials comprises a polymer matrix formed from a crosslinkable polymer mixture. Such a polymer mixture preferably comprises an unsaturated polyolefin (A) comprising a total amount of carbon-carbon double bonds per 1000 carbon atoms of not less than 0.37.

It has been found that such a composite material can be used as a multipurpose substrate.

The use of unsaturated polyolefins in the polymer blend allows the polymer blend to be crosslinkable. This is preferably caused by a double bond present in the polymer mixture. At this time, the degree of crosslinking can be controlled by these double bonds based on the number of carbon-carbon double bonds in the polyolefin as well as the polymer mixture. However, the degree of crosslinking determines the flexibility and / or stiffness of the polymer. Polymers having a high degree of crosslinking also have a higher stiffness than polymers having a low degree of crosslinking. Thus, the composite material according to the present invention can be used in a wide variety of applications.

It is also preferable that the crosslinkable polymer mixture contains the additional copolymer (B).

As used herein, the term "total amount of carbon-carbon double bonds" with respect to the term "unsaturated polyolefin (A)" relates to double bonds derived from vinyl, vinylidene and / or trans-vinylene groups. The amount of any type of double bond is determined according to the procedure as described in the experimental part of EP 1 731 566.

The crosslinking property of the polymer mixture can be controlled by the introduction of a double bond, and the desired degree of crosslinking can be adjusted.

The total content of carbon-carbon double bonds per 1000 carbon atoms is preferably at least 0.40 for various applications. The content of 0.45 to 0.80 per 1000 carbon atoms is particularly advantageous.

Also, the total content of vinyl groups in the unsaturated polyolefin is preferably greater than 0.11 per 1000 carbon atoms. Here, the range of 0.15 to 0.80 per 1000 carbon atoms is particularly preferred, but may be higher.

It is known that there are two kinds of vinyl groups among the polymers. One species is produced in the polymerization process by the beta-cleavage reaction of the secondary radical, or is the result of a so-called chain transfer agent. A second class preferred in the present invention is produced by polymerization between at least one olefin monomer and at least one polyunsaturated monomer.

Both of the vinyl groups may be included in the polymer mixture of the present invention. However, it is preferred that the content of the vinyl group formed by the polymerization between the at least one olefin monomer and the at least one polyunsaturated monomer is at least 0.03 per 1000 carbon atoms. The content is preferably 0.06 to 0.40 per 1000 carbon atoms.

Unsaturated polyolefins in the present invention can be single modal and multimodal, such as bimodal, and can range from 0.860 to 0.960 g / cm3, preferably from 0.880 to 0.955 g / cm3, most preferably from 0.900 to 0.950 g / Cm < 3 >.

It is also preferred that the unsaturated polyolefin is prepared by polymerization from an olefinic monomer, preferably ethylene and propylene, and at least one polyunsaturated monomer.

Here, the polymerization can be carried out by any known method, but radical polymerization at high pressure is preferably used, as described in more detail in WO 93/08222.

It is also preferred that the unsaturated polyolefin comprises at least 60% by weight of ethylene monomer. The content is more preferably at least 70% by weight, particularly preferably at least 80% by weight, most preferably at least 90% by weight.

The highly unsaturated comonomer is preferably a diene. Particularly preferred are dienes selected from the group consisting of

A monomer having a heteroatom-free carbon chain comprising at least eight carbon atoms, at least four carbon atoms being between the unconjugated double bonds and at least one of the double bonds being in the terminal position,

Siloxane according to formula (I)

Wherein R 1 and R 2 can be different or similar alkyl groups composed of 1 to 4 carbon atoms and alkoxy groups having 1 to 4 carbon atoms and n being 1 to 200.

- alpha, omega -divinyl ether according to formula II

Wherein R is - (CH ₂ ) _m -O-, or - (CH ₂ CH ₂ O) _n - or -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-, m is 2 to 10 and n Lt; / RTI >

Dienes can be used in all possible combinations.

The dienes used in the present invention and their preparation are described in more detail in WO 93/08222, WO 96/35732 and WO 97/45465, which are incorporated herein by reference.

It is particularly preferred that the diene is selected from the group consisting of: 1.7-octadiene; 1,9-decadiene; 1,11-dodecadien; 1,13-tetradecadienes; Tetra-methyl divinyl disiloxane; Divinylpoly (dimethylsiloxane); And 1,4-butadiene divinyl ether or combinations thereof.

In addition to the polyunsaturated monomers, additional comonomers such as, for example, C ₃ to C ₂₀ alpha-olefins such as propylene, 1-butene, 1-hexene and 1-butene, or other comonomers such as alkyl acrylates, alkyl methacrylates And polar comonomers such as vinyl acetate may be used in the polymerization.

However, the content of polar monomers in the unsaturated polyolefin (A) is less than 150 micromolar, preferably less than 125 micromolar, particularly preferably less than 100 micromolar.

Further, it is preferable that the polymer mixture further comprises the copolymer (B). The copolymer (B) is preferably polar.

Furthermore, polar copolymers (B) such as unsaturated polyolefins may comprise the compounds described above and thus may comprise the corresponding number of carbon-carbon double bonds. The crosslinking properties of the polymer mixture are thereby still increased.

Here, the content of carbon-carbon double bonds in the polar copolymer is at least 0.15 per 1000 carbon atoms. The content of 0.20 to 0.35 per 1000 carbon atoms is preferred.

However, polar copolymers contain at least 500 micromoles, preferably at least 700 micromoles, particularly preferably at least 900 micromoles, and most preferably at least 1100 micrograms per gram of polar copolymer, It is distinguished by the quantity of moles itself.

Polar copolymers are prepared by polymerization from olefins, preferably ethylene and polar comonomers. Here, there may be at least one or a mixture thereof of the highly unsaturated monomers described above.

Preferably, the polar comonomer is a C ₃ to C ₂₀ monomer, for example, a hydroxyl group, an alkoxy group, a carbonyl group, a carboxyl group, an ester group, or a combination thereof.

Also preferably, the monomer units are selected from the group consisting of alkyl acrylates, alkyl methacrylates and vinyl acetates.

Particularly preferably, the comonomer is a comonomer selected from the group consisting of C ₁ to C ₆ alkyl acrylates, C ₁ to C ₆ alkyl methacrylates, or vinyl acetate.

Polar monomers from the group consisting of alkyl esters of methacrylic acid such as, for example, methyl, ethyl or butyl methacrylate or vinyl acetate are considered particularly preferred. Because of their thermal stability, acrylate types are preferred.

A polar copolymer (B) is preferably from 0.5 to 70 g / 10 min, more preferably 1 to _{55 g / 10 min, MFR 2} .16 most preferably 1.5 to _{40 g / 10 min / 190 ℃} , Called melt flow rate.

The crosslinkable polymer mixture is preferably prepared by mixing two component-unsaturated polyolefin (A) and polar copolymer (B). An accurate description of the preparation of each component (A) and (B) is given in EP 1,731,566.

The crosslinkable polymer mixture is preferably 5 to 60% by weight, more preferably 8 to 50% by weight, particularly preferably 10 to 40% by weight, most preferably 15 To 35% by weight of a polar copolymer.

Further, it is preferable that the total content of carbon-carbon double bonds per 1000 carbon atoms of the crosslinkable polymer mixture is 0.30 or more. The total content of carbon-carbon double bonds per 1000 carbon atoms is 0.35; 0.40; 0.45, 0.50; 0.55 or more, particularly preferably 0.60 or more. Here, it is determined based on the content of vinyl, vinylidene and trans-vinylidene groups per 1000 carbon atoms of both the unsaturated polyolefin (A) and the polar copolymer (B).

Here, the content of the vinyl group is preferably from 0.05 to 0.45, more preferably from 0.10 to 0.40, and particularly preferably from 0.15 to 0.35, per 1000 carbon atoms.

In the present invention, the polymer matrix is formed by crosslinking the above-described crosslinkable polymer mixture.

This is preferably carried out with a crosslinking agent. These agents regenerate the radicals and, as a result, initiate the crosslinking reaction. Compounds containing at least one -O-O- or one -N = N-bond are particularly preferred agents. The use of peroxides is particularly preferred.

Di-tert-amyl peroxide; 2,5-di (tert-butylperoxy) -2,5-dimethyl-3-hexane; 2,5-di (tert-butylperoxy) -2,5-dimethylhexane, tert-butylcumyl peroxide; Di (tert-butyl) peroxide; Dicumyl peroxide; Di (tert-butylperoxide-iso-propyl) benzene, butyl-4,4-bis (tert-butylperoxy) valerate; 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane; Tert-butyl peroxybenzoate, di-benzoyl peroxide are suitable, for example, as peroxides.

The antimicrobial active material is preferably mixed prior to the crosslinking reaction, together with the polymeric matrix, to form a composite material.

Here, it is preferable that the material according to the present invention is contained in the plastic material, especially in the polymer matrix described above in an amount of 0.1 to 50% by volume. A particularly advantageous embodiment is 3 to 15% by volume.

The crosslinking reaction takes place under conventional conditions, for example at a temperature of at least 160 캜.

The crosslinked polymer matrix preferably has an elongation at break, so-called hot-set elongation, of less than 175%, more preferably less than 100%, particularly preferably less than 90%, which is in accordance with IEC 60811-2 -1 method. The value of the elongation at break is related to the degree of crosslinking. The lower the elongation at fracture, the higher the degree of crosslinking of the polymer mixture.

The stiffness of the crosslinked and thus the polymer blend can be controlled by the amount of double bonds and the amount of radical initiator, as already mentioned.

Highly crosslinked polyethylene is desirable in many applications.

The composite material according to the present invention can be easily produced by injection molding. The blended granules in the extruder are preferably used in the production of injection-molded composite materials and are subject to crosslinking reactions. In contrast to the production of polymer matrix composites made with silver nanopowder, if the material according to the invention is used, the carrier for the active material can be abandoned to avoid the formation of agglomerates or clusters.

In addition to the individually adjustable crosslinks and the various applicability thereof, the polymer matrix used in the composite also has good mechanical and thermal stability, for example as described below.

Molybdenum oxide, pre-oxidized molybdenum, tungsten oxide, pre-tungsten oxide, molybdenum-copper, tungsten-copper, molybdenum-silver and tungsten-silver as additives for plastic materials and / It has excellent antimicrobial effect on the material. It was possible to obtain the best results with molybdenum-copper, tungsten-copper, molybdenum-silver and tungsten-silver. Here again, the chemically inactive metal should proceed from the assumption that it promotes the oxidation of the non-inactive metal, thereby promoting the production of hydrogen ions as a result. It is again important to note that if molybdenum-copper, tungsten-copper, molybdenum-silver or tungsten-silver composite powders are used as additives, the molybdenum and / or tungsten phases and copper and / or silver phases are present in very fine form. Composite powders prepared by a coating process may be used, for example. The particle size of the composite powder is preferably smaller than 5 占 퐉.

The material according to the invention may also be present in combination with one or several ceramic materials. The production takes place, for example, by hot compression. Alumina, titanium oxide, silicon oxide, silicon carbide and zirconium oxide are particularly suitable as ceramic phase. In order to be able to use general production methods and conditions of ceramics, additives according to the present invention which are present in the highest oxidation state such as, for example, MoO ₃ and WO ₃ , are suitable. In addition, metal molybdenum and tungsten may still be present.

Therefore, a combination of the following materials results in a suitable ceramic composite material: Al ₂ O ₃ -MoO ₃ , Al ₂ O ₃ -WO ₃ , ZrO ₂ -MoO ₃ , ZrO ₂ -WO ₃ , Al ₂ O ₃ -Mo-MoO _{3, Al 2 O 3 -W-} WO 3, ZrO 2 -Mo-MoO 3, ZrO 2 -W-WO 3, TiO 2 -MoO 3, TiO 2 -WO 3, TiO 2 -Mo-MoO 3, TiO 2 _{-W-WO 3, SiO 2 -MoO} 3, SiO 2 -WO 3, SiO 2 -Mo-MoO 3 and SiO _{2 -} W-WO _3. Here, the favorable fraction of MoO ₃ or WO ₃ is 0.001 to 50 mol%. The advantageous molar ratio of ZrO ₂ , Al ₂ O ₃ , TiO ₂ or SiO ₂ to MoO ₃ or WO ₃ is 1 to 100.

Due to its high antimicrobial effect, a number of favorable applications are made to the substances according to the invention. This includes implants and other devices for medical technology. However, with respect to implants, materials according to the present invention can be used particularly advantageously in catheters, stents, bone implants, dental implants, vascular implants and in-vitro prosthetic implants.

Advantageous applications in the catheter field include port catheters and bladder catheters. The port catheter generally includes a chamber having a silicon membrane and a connecting tube. Until now, the chamber is generally made of plastic material, plastic covered with titanium or ceramics. Now, the chamber of the catheter or catheter may be made from a material according to the invention or from a material comprising such a material. However, it is also possible to provide a catheter having a layer according to the present invention or a portion thereof. If the chamber is composed of molybdenum-silver and the silver content is 1 to 40% by weight, very good results can be achieved. According to the prior art, this chamber is again covered with a plastic material. It is also advantageous if the plastic material and / or the silicon film comprise a material.

Problems with bacterial contamination can also occur with Luerlock connections, three-way cocks and cock benches, and these are therefore the preferred applications for the material according to the invention .

For the coronary stent, it is advantageous to apply the material according to the invention by a coating process on a stent made of a shape memory alloy, for example, Nitinol. The material according to the invention may also be advantageously used in urinary stents. Urinary stents are generally made from polyurethane or silicone. Here, the substance according to the present invention can be added to the polymeric material, or can be applied again as a layer on the surface.

Bone implants contact tissue fluid. Here, the substance according to the present invention can also exhibit its effect. Here, it is advantageous to apply the substance according to the invention as a layer. An example of a bone implant is the hip joint. It is advantageous to make the layer smooth at the joints, while the implant axis may have a sponge coating. As already mentioned, it is also suitable to obtain an antimicrobial effect in vascular inserts or in the hernia membranes, since the substances according to the invention can easily be bound to a polymeric material. Medical-technical uses also include surgical uses.

In addition, the material according to the present invention can be used in any kind of container used in medicine. Due to the high risk of microbial contamination, the use of the substances according to the invention is advantageous in nasal spray containers.

In addition to pure medical and veterinary use, many applications in the hygiene are possible. The material is suitable as an additive to absorbent sanitary articles or wound dressings. Sanitary appliances and wound dressings include polymer fibers or lattices. Now, the material according to the invention can advantageously be deposited on the surface of fibers and / or lattices, or the fibers and / or lattice may comprise material.

In addition, the substances according to the present invention can also be used to enhance these antimicrobial effects or to provide a longer period of time, since they are often only of a short-term antimicrobial effect, such as wound dressing spray - also called "liquid wound dressing" It can be used as an additive to maintain it. Here, the use of the material according to the present invention preferably comprises or consists of molybdenum. More preferably, the molybdenum and / or their compounds and alloys thereof are used in a concentration of 0.05 to 1.0% by volume in the wound coating spray, particularly preferably in a concentration of 0.1 to 0.5% by volume.

The materials according to the invention are also suitable as varnishes, coating materials and additives for adhesives. Here, if the varnish, the coating material or the adhesive contains 0.01 to 70% by volume of the substance, the effect is exhibited. A particularly preferable range is from 0.1 to 40% by volume. MoO ₃ and / or WO ₃ are particularly suitable as additives in cost sensitive products. Here, the preferred particle size according to the fisher is 0.5 to 10 mu m. Here, for example, the addition of an inert metal such as silver may be abandoned. However, additives which are based on tungsten-silver, tungsten-copper, molybdenum-silver, molybdenum-copper, molybdenum-tin and tungsten-tin are preferred, especially if high effectiveness is desired. Preferably, the size of the particles according to the Fischer of 0.5 to 10 mu m can be included in a liquid varnish system, such as a two-component polyurethane varnish, by conventional dispersion techniques.

In addition to its application in the medical and hygiene sector, the substances according to the invention can also be used as additives for personal hygiene products. Ointments, soaps, tooth cleaning compositions, toothpastes, adhesive for dentures, toothbrushes, cleansing agents between teeth and tooth cleaning chews are referred to herein as advantageous products.

In addition, the material according to the invention can also be advantageously used as an adhesive for filters. Here, metal composites that have proved to be particularly valuable include inert phases such as, for example, silver, copper or tin in addition to tungsten or molybdenum. Here, the filter may be composed of a polymer fiber containing the substance again or coated with the substance.

Currently, antimicrobial active substances are already used as additives for clothing products and shoe insole. In these applications, it can also be used advantageously at a lower cost than silver nano. Here, the polymer fiber may include a substance, or the substance may exist in the form of being deposited on the polymer fiber.

Since the materials according to the invention can be easily mixed with varnishes, coating materials and / or plastic materials, the products thus manufactured are suitable as furnishings, in particular sanitary ware.

In addition to these applications, there are many more applications for materials in accordance with the present invention, particularly for products in daily life. This includes, for example, parts of switches, parts, credit cards, keyboards, cell phone housings, coins, banknotes, door handles and public transport fixtures. A more favorable application is to use it as a component for air conditioning systems. The material according to the invention is suitable for air conditioning of transporting institutions, for example automobiles. Generally, a heat-radiating fin made of an aluminum alloy can be advantageously coated with the material according to the present invention. The axis of the air conditioning system in the building can also be designed in an antibacterial manner by adding the active material to the shaft material or by coating the shaft material with it. Air humidifiers can also have corresponding antibacterial properties.

It is also preferred that the material according to the invention is used in cables, in particular cables comprising polyurethane.

They represent only such a list as an example of a possible advantageous application. The material according to the invention can also be used in all cases where silver nano is already used or where people have already begun to think about it. It should be considered here that the requirements for satisfying antimicrobial effect, clotting and cytotoxicity depend on the application field.

The present invention is further characterized in that:

1. A composite material made of an antimicrobial active material comprising molybdenum and / or tungsten and one or more materials, wherein the at least one material comprises a polymer matrix formed from a crosslinkable polymer mixture, wherein the crosslinkable polymer mixture comprises carbon atoms (A) having a total amount of carbon-carbon double bonds per 100 carbon atoms of not less than 0.37.

2. The composite material according to claim 1, wherein the crosslinkable polymer mixture further comprises a copolymer (B).

3. The composite material according to claim 1 or 2, wherein the volume content of the material in the composite material is 0.1 to 50% by volume.

4. The composite material according to any one of claims 1 to 3, wherein the surface of the material is at least partially oxidized.

5. The composite material according to any one of claims 1 to 4, wherein the material is molybdenum oxide or tungsten oxide.

6. The composite material according to any one of claims 1 to 4, wherein the material is a molybdenum, molybdenum alloy and / or molybdenum compound, and the surface has a molybdenum oxide layer.

7. The composite material according to any one of claims 1 to 4, wherein the material is a tungsten, tungsten alloy and / or tungsten compound, and the surface has a tungsten oxide layer.

8. The molybdenum compound according to claim 6, wherein the molybdenum compound is a compound of molybdenum and 0.1 to 1 wt% La ₂ O ₃ , molybdenum and 0.5 wt% Ti, 0.08 wt% Zr, 0.01 to 0.04 wt% To 50% by weight of Re, or a compound of molybdenum and 1.2% by weight of Hf and 0.02 to 0.15% by weight of C, respectively.

9. The composite material according to claim 6, wherein the molybdenum compound is molybdenum carbide, molybdenum nitride, molybdenum silicide and / or molybdenum sulfide.

10. The composite material according to claim 7, wherein the tungsten alloy is an alloy of tungsten, 0.1 to 1 wt% La ₂ O ₃ , or tungsten and 1 to 26 wt% Re.

11. The composite material according to claim 7, wherein the tungsten compound is tungsten carbide, tungsten nitride, tungsten silicide, and / or tungsten sulfide.

12. The composite material according to any one of claims 1 to 11, wherein the unsaturated polyolefin (A) of the crosslinkable polyolefin mixture is prepared by polymerization of an olefin monomer and at least one polyunsaturated monomer.

13. The composite material according to claim 12, wherein the olefin monomer is ethylene.

14. The composite material of claim 12, wherein the polyunsaturated monomer is a diene.

15. The composite material according to claim 14, wherein the polyunsaturated component is composed of any one of the following a), b), c) and d):

a) a carbon chain which is free of heteroatoms and contains at least 8 carbon atoms, at least 4 carbon atoms being between unconjugated double bonds and at least one of which is in the terminal position, or

b) alpha, omega -divinylsiloxane according to formula I

Wherein R < ₁ > and R < ₂ > are an alkyl group having 1 to 4 carbon atoms and different or similar carbon atoms and an alkoxy group having 1 to 4 carbon atoms, n is 1 to 200,

c) an alpha, omega -divinyl ether according to formula II

Wherein R is - (CH ₂ ) _m -O-, or - (CH ₂ CH ₂ O) _n - or -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-, m is 2 to 10, n is from 1 to 5,

d) or a mixture of a), b) and / or c)

16. The composite material according to any one of claims 1 to 15, wherein the copolymer (B) is polar.

17. The composite material of claim 16, wherein the polar copolymer is prepared by polymerization of one olefin and at least one polar copolymer.

18. Use as an article for avoiding bacterial propagation of the composite material according to any one of claims 1 to 17.

19. Use according to claim 18, characterized in that the article is a medical product.

20. Use according to claim 19, characterized in that the product is a port catheter comprising a chamber with a silicon membrane and a connecting tube, said chamber and / or tube being composed of a composite material according to any one of claims 1 to 17. .

21. Use according to claim 20, characterized in that the product is a Luerlock connection, three-way cock and / or cocktail.

The invention is illustrated in more detail in the following examples.

Table 1 shows the instructions for the preparation of the samples.

Table 2 shows the effect on Staphylococcus aureus, Table 3 shows the effect on E. coli, and Table 4 shows the effect on P. aeruginosa.

The irradiated materials are shown in Table 1. Table 1 also includes a schematic description of the composition of the starting material and sample preparation. The compression process was carried out by die pressing at a compression pressure of about 250 MPa for the samples W 02, W 03, W 04, W 05, Mo 02, Mo 03, Mo 04 and Mo 05 according to the present invention. . The sintering process was performed on these samples at a temperature of 850 ° C for 60 minutes under pure hydrogen conditions in a tungsten tube electric furnace. Unalloyed tungsten (sample W 09) and unalloyed molybdenum (sample Mo 09) were compressed in an isostatic manner at 220 MPa and sintered at 2250 ° C for 4 hours and / or at 2100 ° C for 4 hours, followed by a roll bending process The degree of deformation was about 70%.

Transoptic. Acylic resins derived from Buhler have generally been used as polymer matrices for the preparation of polymer matrix composites used in the manufacture of polished pieces. Atmospheric plasma spraying was used for the deposition of molybdenum layers (samples SL 50, SL 51, SL 52). Here, the layer thickness was approximately 100 mu m, and the layer density was theoretically 85% of the density. Because the coating process was performed in air, the oxygen content in the layer was approximately 1.5 wt%. Here, the oxygen mainly exists in the form of MoO ₃ . The molybdenum layer was deposited on a titanium alloy (SL 50), niobium (SL 51), and intermetallic material (SL 52).

20% copper powder (SL 20) embedded in a plastic matrix, 50% copper powder (SL 20) embedded in a plastic matrix, embedded in a plastic matrix, non-alloyed copper (Cu 01) 20 wt% silver (SL 21) and 50 wt% silver (SL 27) embedded in a plastic matrix were used as comparative samples. In addition, the antimicrobial effectiveness of a number of additional materials based on niobium, tantalum and titanium has been measured for comparison purposes.

The previously described roll-out incubation was used to investigate the antimicrobial effect. The experiment was carried out separately for Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus. For this purpose, an active-substance sample was added to the bacterial suspension. Bacterial growth occurred on the surface. Samples were rolled throughout the so-called agar medium after 3, 6, 9 and 12 hours and added to sterile physiological saline. After this rolling process, a photograph of the agar medium was taken and evaluated for bacterial-reducing and / or bactericidal effects. The evaluation of photos and effects on Staphylococcus aureus is shown in Table 2, Escherichia coli in Table 3, and Pseudomonas aeruginosa in Table 4.

Here, it can be seen that all materials based on tungsten or molybdenum are at least equal to, or partly obviously surpassing, at least the dense form of sterling silver for its antimicrobial effect. It has been proved that the sample contains silver or copper in addition to molybdenum, or silver or copper other than tungsten is particularly effective.

Polymer matrix composites containing molybdenum oxide or tungsten oxide also have to be evaluated as having a good antimicrobial effect. The use of powders of fine particles, preferably with a particle size according to a physis of less than 5 mu m, is advantageous.

Except for samples mixed with copper, samples based on tantalum or niobium have no effect. However, the high antimicrobial effect of copper with cytotoxicity results in tantalum-copper and niobium-copper.

The effect of the titanium-based comparative sample should also be evaluated negatively.

Testing with polymeric matrix materials shows that the effect can be controlled by the amount and particle size of the molybdenum and / or tungsten powder to which it is added. The finer the molybdenum and / or tungsten powder, the higher their effect (SL 33, SL 34). Here, the molybdenum oxide powder has a better antimicrobial effect than the molybdenum metal powder (SL 22, SL 33).

In addition to the samples described here, niobium oxide, silicon carbide, and manganese oxide have antibacterial effects that can contribute to lowering the pH value.

Furthermore, the first test for cytotoxicity was also performed. It has become clear that all copper-containing materials are cytotoxic. The first test for clotting was also performed. Silver-containing tungsten alloys have higher coagulation properties than silver-containing molybdenum alloys. However, it should be noted that the quality of the surface also affects the results.

Tests of water-soluble molybdenum and tungsten salts were also carried out to determine the mechanism of action. For this purpose, the test described above was carried out in a plastic matrix of sodium molybdate (Na ₂ MoO ₄ ) and tungsten molybdate (Na ₂ WO ₄ ) plastics in order to measure the antimicrobial effect.

Here, the pH of the physiological saline solution was not lowered. The samples were ineffective in antibacterial activity. At that time, the content of the component dissolved in the saline solution was measured after an age hardening time of 24 hours. As expected, these values are very high for water-soluble compounds. The content of molybdenum in the saline solution of 50 mg / l cm 2 was measured, for example, for sodium molybdate. As a comparative method, the values for antibacterial active materials are 0.1 (sample SL 18), 0.4 (sample SL 22), and 0.4 mg / 1 · cm 2 (sample SL 24). Therefore, the antimicrobial effect is not related to the content of molybdenum or tungsten in the saline solution.

Similar results were also obtained with sodium tungstate. Here, the content of tungsten in the saline solution was 324 mg / l · cm 2. As an example, a value of 0.1 for sample SL 17, a value of 0.3 for sample SL 19 and a value of 0.9 mg / 1 ㎠ 2 for sample SL 35 were measured.

After aging for 24 hours in physiological saline, the silver content was measured on silver-containing materials such as tungsten 02 and tungsten 03. Here, the value of tungsten 02 was 28.6 and the value of tungsten 03 was 68.2 mg / l · cm 2.

As is known in the literature, silver acts antimicrobially through the formation of Ag ⁺ ions. The effect increases with increasing silver ion concentration. However, it was impossible to identify any dependence of the antimicrobial effect of molybdenum and tungsten on the content of molybdenum and / or tungsten in physiological saline. Therefore, it must proceed from the fact that it is not active with molybdenum and tungsten itself. Therefore, the pH value of the saline solution was measured after the test was finished. The pH values were almost neutral in materials that did not have any antimicrobial effect such as tantalum, tantalum 05, tantalum-20, niobium, niobium-5, and niobium-20. Sterling silver also does not lower any pH value.

However, it is possible to confirm that the pH value is lowered in all the samples according to the present invention. The pH values of W 09, W 02 and W 03 were 4, 8, 3.3 and 3.1, respectively. For the tungsten carbide samples with 20 wt% silver, 5.3, Mo 09, 4.0, 3.8. Lowering the pH value can contribute to the formation of oxonium ions (H ₃ O ⁺ ). This results from the reaction of H ₂ MoO ₄ and / or H ₂ WO ₄ with water and releases MoO ₄ ^- , MoO ₄ ^{2 -} , WO ₄ ^- or WO ₄ ^{2 -} .

H ₂ MoO ₄ and / or H ₂ WO ₄ are reconstituted from the reaction of MoO ₃ and / or WO ₃ with water and / or dissolved oxygen.

Guidelines for Sample Preparation (1/3) material
[weight%]

(designation) caution Starting material Preparation of sample Non-alloy  tungsten,
Oxidized

(W_09) According to the invention Tungsten powder: Fisher particle size 4.0 μm Compression → sintering → re-molding → mechanical process → oxidation (dense material) Tungsten-5

(W_02) According to the invention Tungsten powder: Fisher particle size 4.0 μm
Silver powder: Fisher particle size 1.0 탆 Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density)
Tungsten-20

(W_03) According to the invention Tungsten powder: Fisher particle size 4.0 μm
Silver powder: Fisher particle size 1.0 탆 Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density)
Tungsten-5 copper

(W_04) According to the invention Tungsten powder: Fisher particle size 4.0 μm
· Copper powder: Fisher particle size 6.9 μm Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density)
tungsten- 20 Copper

(W_05) According to the invention Tungsten powder: Fisher particle size 4.0 μm
· Copper powder: Fisher particle size 6.9 μm Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density) Plastic Matrix + 20 tungsten  powder

( SL _17) According to the invention Tungsten powder: Fisher particle size 4.0 μm
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Plastic Matrix + 50 tungsten  powder

( SL _23) According to the invention Tungsten powder: Fisher particle size 4.0 μm
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Plastic Matrix + 20 ( Tungsten 20 ) powder

( SL _19) According to the invention Tungsten powder: Fisher particle size 4.0 μm
Silver powder: Fisher particle size 1.0 탆
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Plastic Matrix + 50 ( Tungsten 20 ) powder

( SL _25) According to the invention Tungsten powder: Fisher particle size 4.0 μm
Silver powder: Fisher particle size 1.0 탆
· Synthetic resin matrix: Transophytic powder (Acyl resin) of Vigler GmbH & Mixing → compression → mechanical processing Plastic Matrix + 50 WO3  powder

( SL _35) According to the invention WO3 powder: Fisher particle size 12 占 퐉
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Non-alloy  Molybdenum, oxidized

( Mo _09) According to the invention Molybdenum powder: Fisher particle size 3.8 탆 Compression → sintering → re-molding → mechanical process → oxidation (dense material) Molybdenum-5

( Mo _02) According to the invention Molybdenum powder: Fisher particle size 3.8 탆
Silver powder: Fisher particle size 1.0 탆 Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density) Molybdenum-20

( Mo _03) According to the invention Molybdenum powder: Fisher particle size 3.8 탆
Silver powder: Fisher particle size 1.0 탆 Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density) Molybdenum-5 copper

( Mo _04) According to the invention Molybdenum powder: Fisher particle size 3.8 탆
· Copper powder: Fisher particle size 6.9 μm Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density)

Instructions for sample preparation (2/3)

material
[weight%]

(designation) caution Starting material Preparation of sample molybdenum- 20 Copper

( Mo _05) According to the invention Molybdenum powder: Fisher particle size 3.8 탆
· Copper powder: Fisher particle size 6.9 μm Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density) Plastic Matrix + 20 molybdenum  powder

( SL _16) According to the invention Molybdenum powder: Fisher particle size 3.8 탆
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Plastic Matrix + 50 molybdenum  powder
( SL _22) According to the invention Molybdenum powder: Fisher particle size 3.8 탆
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Plastic Matrix + 20 ( The molybdenum 20 ) powder

( SL _18) According to the invention Molybdenum powder: Fisher particle size 3.8 탆
Silver powder: Fisher particle size 1.0 탆
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Plastic Matrix + 50 ( The molybdenum 20 ) powder

( SL _24) According to the invention Molybdenum powder: Fisher particle size 3.8 탆
Silver powder: Fisher particle size 1.0 탆
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Plastic Matrix + 50 MO ₂  powder

( SL _33) According to the invention MoO ₂ powder: Fisher particle size 3.6 탆
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Plastic Matrix + 50 MO ₃  powder

( SL _34) According to the invention MoO ₃ powder: Fischer particle size 15.9 탆
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Titanium-46. 5 aluminum (Chromium, niobium, tantalum, boron), molybdenum

( SL _50) According to the invention · Melting ingots Extrusion → Mechanical Process → Molybdenum Coating by Atmospheric Plasma Spraying Non-alloy  Coated with niobium and molybdenum

( SL _51) According to the invention Niobium powder: Fisher particle size 4.7 탆 Compression → sintering → re-molding → mechanical process → molybdenum coating by atmospheric plasma spraying titanium- 6 Aluminum - 4 Vanadium-2 is coated with molybdenum
( SL _52) According to the invention · Melting ingots Mechanical process → Molybdenum coating by atmospheric plasma spraying Non-alloy  tantalum

( Ta _01) Not according to the invention Tantalum powder: Fisher particle size 11.0 탆 Compression → sintering → re-forming → mechanical process (dense material) Tantal-5

( Ta _02) Not according to the invention Tantalum powder: Fisher particle size 11.0 탆
Silver powder: Fisher particle size 1.0 탆 Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density) Tantalum-20

( Ta _03) Not according to the invention Tantalum powder: Fisher particle size 11.0 탆
Silver powder: Fisher particle size 1.0 탆 Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density) Tantalum-5 copper

( Ta _04) Not according to the invention Tantalum powder: Fisher particle size 11.0 탆
· Copper powder: Fisher particle size 6.9 μm Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density)

Guidelines for sample preparation (3/3)

material
[weight%]

(designation) caution Starting material Production of sample tantalum- 20 Copper

( Ta _05) Not according to the invention Tantalum powder: Fisher particle size 11.0 탆
· Copper powder: Fisher particle size 6.9 μm Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density) Non-alloy  Niobium

( Nb _01) Not according to the invention Niobium powder: Fisher particle size 4.7 탆 Compression → sintering → re-forming → mechanical process (dense material) Niobium-5

( Nb _02) Not according to the invention Niobium powder: Fisher particle size 4.7 탆
Silver powder: Fisher particle size 1.0 탆 Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density) Niobium-20

( Nb _03) Not according to the invention Niobium powder: Fisher particle size 4.7 탆
Silver powder: Fisher particle size 1.0 탆 Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density) Niobium-5 copper

( Nb _04) Not according to the invention Niobium powder: Fisher particle size 4.7 탆
· Copper powder: Fisher particle size 6.9 μm Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density) Niobium- 20 Copper

( Nb _05) Not according to the invention Niobium powder: Fisher particle size 4.7 탆
· Copper powder: Fisher particle size 6.9 μm Mixing → compression → sintering → mechanical process (porous material: theoretically 60-70% of density) titanium- 6 Aluminum -4 bar Nidium -2 is

( IM - Ti _01) Not according to the invention · Melting ingots Mechanical process Titanium-46. 5 Alu 4 (chromium, niobium, tantalum, boron)

( IM - TiAl _01) Not according to the invention · Melting ingots Extrusion → mechanical process Non-alloy  Copper

( Cu _01) Conventional technology Reformed copper rod Mechanical process Non-alloy  silver

( SL _14) Conventional technology · Re-Formed Silver Pipe Mechanical process Plastic Matrix + 20 Copper  powder

( SL _20) Conventional technology · Copper powder: Fisher particle size 6.9 μm
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Plastic Matrix + 50 Copper Powder

( SL _26) Conventional technology · Copper powder: Fisher particle size 6.9 μm
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Plastic matrix + 20 silver powder

( SL _21) Conventional technology Silver powder: Fisher particle size 1.0 탆
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing Plastic matrix + 50 silver powder

( SL _27) Conventional technology Silver powder: Fisher particle size 1.0 탆
· Plastic Matrix: Transophytic powder from Vigler GmbH & Co. KG (acyl resin) Mixing → compression → mechanical processing

Effect on Staphylococcus aureus (1/3) material
[weight%]

(designation) caution Effect
evaluation Effect after each hour 0h 3h 6h 9h 12h Non-alloy  Tungsten, oxidized
(W_09) According to the invention Satisfaction

Tungsten-5

(W_02) According to the invention good

Tungsten-20

(W_03) According to the invention Very good

Tungsten-5 copper

(W_04) According to the invention Very good

tungsten- 20 Copper

(W_05) According to the invention Very good

Plastic Matrix + 20 tungsten  powder
( SL _17) According to the invention good

Plastic Matrix + 50 tungsten  powder
( SL _23) According to the invention good

Plastic Matrix + 20 ( Tungus Ten 2 0 is )powder
( SL _19) According to the invention Satisfaction

Plastic Matrix + 50 ( Tungsten 20 )powder
( SL _25) According to the invention good

Plastic Matrix +50 WO ₃ powder
( SL _35) According to the invention Satisfaction

Non-alloy  Molybdenum, oxidized
( Mo _09) According to the invention good

Molybdenum-5

( Mo _02) According to the invention Very good

Molybdenum-20

( Mo _03) According to the invention Very good

Molybdenum-5 copper

( Mo _04) According to the invention Very good

Effect on Staphylococcus aureus (2/3)

material
[weight%]

(designation) caution Effect
evaluation Effect after each hour 0h 3h 6h 9h 12h molybdenum- 20 Copper

( Mo _05) According to the invention Very good

Plastic Matrix + 20 moly rib Den powder
( SL _16) According to the invention good

Plastic Matrix + 50 molyb Den powder
( SL _22) According to the invention good

Plastic Matrix +20 ( Molyb Den 2 0 is ) powder
( SL _18) According to the invention good

Plastic Matrix +50 (mall Libden 20) powder
( SL _24) According to the invention good

Plastic Matrix +50 MO ₂  powder
( SL _33) According to the invention good

Plastic Matrix +50 MO ₃ powder
( SL _34) According to the invention Very good

Titanium-46. 5 eggs Coated with aluminum-4 (chromium, niobium, tantalum, boron), molybdenum
( SL _50) According to the invention Very good

Non-alloy  Coated with niobium and molybdenum
( SL _51) According to the invention good

titanium- 6 aluminum ≪ / RTI & 4 vanadium -2 is coated with molybdenum
( SL _52) According to the invention good

Non-alloy  tantalum
( Ta _01) Not according to the invention Poor

Tantal-5
( Ta _02) Not according to the invention Poor

Tantalum-20

( Ta _03) Not according to the invention Poor

Tantalum-5 copper

( Ta _04) Not according to the invention Very good

Effect on Staphylococcus aureus (3/3)

material
[weight%]

(designation) caution Effect
evaluation Effect after each hour 0h 3h 6h 9h 12h tantalum- 20 Copper

( Ta _05) Not according to the invention Very good

Non-alloy  Niobium

( Nb _01) Not according to the invention Poor

Niobium-5

( Nb _02) Not according to the invention Poor

Niobium-20

( Nb _03) Not according to the invention Poor

Niobium-5 copper

( Nb _04) Not according to the invention Very good

Niobium- 20 Copper

( Nb _05) Not according to the invention Very good

titanium- 6 Aluminum - 4 vanadium -2 is
( IM - Ti _01) Not according to the invention Poor

Titanium-46. 5 aluminum 4 (chromium, niobium, tantalum, boron)
( IM - TiAl _01) Not according to the invention Poor

Non-alloy  Copper

( Cu _01) Conventional technology good

Non-alloy  silver

( SL _14) Conventional technology Satisfaction

Plastic Matrix + 20 Copper  powder
( SL _20) Conventional technology Very good

Plastic Matrix + 50 Copper  powder
( SL _26) Conventional technology Very good

Plastic matrix +20 silver powder
( SL _21) Conventional technology good

Plastic matrix + 50 silver powder
( SL _27) Conventional technology good

Effect on E. coli (1/3) material
[weight%]

(designation) caution Effect
evaluation Effect after each hour 0h 3h 6h 9h 12h Non-alloy  tungsten,
Oxidized
(W_09) According to the invention Satisfaction

Tungsten-5

(W_02) According to the invention Very good

Tungsten-20

(W_03) According to the invention Very good

Tungsten-5 copper

(W_04) According to the invention Very good

tungsten- 20 Copper

(W_05) According to the invention Very good

Plastic Matrix +20 Tongue Sten  powder

( SL _17) According to the invention Not investigated Not investigated Plastic Matrix +50 Tongue Sten  powder

( SL _23) According to the invention Not investigated Not investigated Plastic Matrix +20 (Tongue Sten 20) powder
( SL _19) According to the invention Not investigated Not investigated Plastic Matrix +50 (Tongue Sten 20) powder
( SL _25) According to the invention Not investigated Not investigated Plastic Matrix + 50 WO ₃  powder

( SL _35) According to the invention Not investigated Not investigated Non-alloy  Molybdenum, oxidized
( Mo _09) According to the invention Satisfaction

Molybdenum-5

( Mo _02) According to the invention Very good

Molybdenum-20

( Mo _03) According to the invention Very good

Molybdenum-5 copper

( Mo _04) According to the invention Very good

Effect on E. coli (2/3)

material
[weight%]

(designation) caution Effect
evaluation Effect after each hour 0h 3h 6h 9h 12h molybdenum- 20 Copper

( Mo _05) According to the invention Very good

Plastic +
20 molybdenum  powder

( SL _16) According to the invention Not investigated Not investigated Plastic Matrix +50 moles Libden  powder

( SL _22) According to the invention Not investigated Not investigated Plastic Matrix +20 (mall Libden 20) powder
( SL _18) According to the invention Not investigated Not investigated Plastic Matrix +50 (mall Libden 20) powder
( SL _24) According to the invention Not investigated Not investigated Plastic Matrix + 50MO ₂  powder
( SL _33) According to the invention Not investigated Not investigated Synthetic resin matrix + 50MO ₃  powder
( SL _34) According to the invention Not investigated Not investigated Titanium-46. 5 aluminum Coated with chromium-4 (chromium, niobium, tantalum, boron) molybdenum
( SL _50) According to the invention good

Non-alloy  Niobium,
Coated with molybdenum
( SL _51) According to the invention Satisfaction

titanium- 6 Aluminum - 4 Vanadium-2 is coated with molybdenum
( SL _52) According to the invention Not investigated Not investigated Non-alloy  tantalum

( Ta _01) Not according to the invention Poor

Tantal-5

( Ta _02) Not according to the invention Poor

Tantalum-20

( Ta _03) Not according to the invention Poor

Tantalum-5 copper

( Ta _04) Not according to the invention good

Effect on E. coli (3/3)

material
[weight%]

(designation) caution Effect
evaluation Effect after each hour 0h 3h 6h 9h 12h tantalum- 20 Copper

( Ta _05) Not according to the invention good

Non-alloy  Niobium

( Nb _01) Not according to the invention Poor

Niobium-5

( Nb _02) Not according to the invention Poor

Niobium-20

( Nb _03) Not according to the invention Poor

Niobium-5 copper

( Nb _04) Not according to the invention good

Niobium- 20 Copper

( Nb _05) Not according to the invention good

titanium- 6 Aluminum - 4 vanadium -2 is

( IM - Ti _01) Not according to the invention Poor

Titanium-46. 5 Aluminum -4 (chromium, niobium, tantalum, boron)
( IM - TiAl _01) Not according to the invention Poor

Non-alloy  Copper

( Cu _01) Conventional technology Satisfaction

Non-alloy  silver

( SL _14) Conventional technology Satisfaction

Plastic matrix + 20 spheres Lee  powder

( SL _20) Conventional technology Not investigated Not investigated Plastic matrix + 50 spheres Lee  powder

( SL _26) Conventional technology Not investigated Not investigated Plastic matrix + 20 silver powder

( SL _21) Conventional technology Not investigated Not investigated Plastic matrix + 50 silver powder

( SL _27) Conventional technology Not investigated Not investigated

Effects on Pseudomonas aeruginosa (1/3) material
[weight%]

(designation) caution Effect
evaluation Effect after each hour 0h 3h 6h 9h 12h Non-alloy  tungsten,
Oxidized
(W_09) According to the invention Satisfaction

Tungsten-5

(W_02) According to the invention Very good

Tungsten-20

(W_03) According to the invention Very good

Tungsten-5 copper

(W_04) According to the invention Very good

tungsten- 20 Copper

(W_05) According to the invention Very good

Plastic Matrix + 20 Tong Sten  powder

( SL _17) According to the invention Satisfaction

Plastic Matrix + 50 Tongue Sten  powder

( SL _23) According to the invention Satisfaction

Plastic Matrix + 20 (Tongue Sten2 0) powder
( SL _19) According to the invention Satisfaction

Plastic Matrix + 50 (Tongue Sten2 0) powder
( SL _25) According to the invention Satisfaction

Plastic Matrix + 50WO ₃  powder
( SL _35) According to the invention Poor

Non-alloy  molybdenum,
Oxidized
( Mo _09) According to the invention Very good

Molybdenum-5

( Mo _02) According to the invention Very good

Molybdenum-20

( Mo _03) According to the invention Very good

Molybdenum-5 copper

( Mo _04) According to the invention Very good

Effect on Pseudomonas aeruginosa (2/3)

material
[weight%]

(designation) caution Effect
evaluation Effect after each hour 0h 3h 6h 9h 12h molybdenum- 20 Copper

( Mo _05) According to the invention Very good

Plastic Matrix + 20 moles Libden  powder

( SL _16) According to the invention Satisfaction

Plastic Matrix + 50 moles Libden  powder

( SL _22) According to the invention Satisfaction

Plastic Matrix + 20 (mall Libden 2 0) powder
( SL _18) According to the invention Satisfaction

Plastic Matrix + 50 (Mall Libden 2 0)
powder
( SL _24) According to the invention Satisfaction

Plastic Matrix + 50MO ₂  powder
( SL _33) According to the invention good

Plastic Matrix + 50MO ₃  powder
( SL _34) According to the invention Very good

Titanium-46. 5 Aluminum -4 (chromium, niobium, tantalum, boron), molybdenum
( SL _50) According to the invention good

Non-alloy  Niobium, molybdenum
Coated with brass
( SL _51) In the present invention
Following
good

titanium- 6 Aluminum - 4 Vanadium-2 is coated with molybdenum
( SL _52) According to the invention Not investigated Not investigated Non-alloy  tantalum

( Ta _01) Not according to the invention Poor

Tantal-5

( Ta _02) Not according to the invention Poor

Tantalum-20

( Ta _03) Not according to the invention Poor

Tantalum-5 copper

( Ta _04) Not according to the invention good

Effect on Pseudomonas aeruginosa (3/3)

material
[weight%]

(designation) caution Effect
evaluation Effect after each hour 0h 3h 6h 9h 12h tantalum- 20 Copper

( Ta _05) Not according to the invention good

Non-alloy  Niobium

( Nb _01) Not according to the invention Poor

Niobium-5

( Nb _02) Not according to the invention Poor

Niobium-20

( Nb _03) Not according to the invention Poor

Niobium-5 copper

( Nb _04) Not according to the invention good

Niobium- 20 Copper

( Nb _05) Not according to the invention good

titanium- 6 Aluminum - 4 vanadium -2 is
( IM - Ti _01) Not according to the invention Poor

Titanium-46. 5 Aluminum -4 (chromium, niobium, tantalum, boron)
( IM - TiAl _01) Not according to the invention Not investigated Not investigated Non-alloy  Copper

( Cu _01) Conventional technology Very good

Non-alloy  silver

( SL _14) Conventional technology Satisfaction

Plastic matrix + 20 spheres Lee  powder
( SL _20) Conventional technology Very good

Plastic matrix + 50 spheres Lee  powder
( SL _26) Conventional technology Very good

Plastic matrix + 20 silver powder
( SL _21) Conventional technology Satisfaction

Plastic matrix + 50 silver powder
( SL _27) Conventional technology Satisfaction

Claims (52)

A method for reducing microbial growth using an inorganic material comprising MoO ₂ , MoO _3, or a combination thereof, which forms an antimicrobial effect upon formation of hydrogen cations upon contact with a water-soluble medium, said material being present as a layer or a component of a layer Wherein the material is present as a composite material in combination with at least one material, the composite material comprising a polymeric matrix, wherein the material is included in the composite material at 3 to 50 weight percent. The method of claim 1, wherein the aqueous medium is water, a solution, or a suspension. The method of claim 1, wherein the aqueous medium is a body fluid or a liquid tissue. The method of claim 1, wherein the aqueous medium is present in the form of a water film adsorbed onto the surface of the material. The method of claim 1, wherein the pH value of the aqueous medium is less than 6.0 by formation of hydrogen cations. The method of claim 1, wherein the solubility of the material in the aqueous medium is less than 0.1 mole / l. The method of claim 1 wherein there is a further phase, which is a chemically inert metal. 8. The method of claim 7, wherein the phase is silver, copper, tin, or an alloy of these metals. delete The method of claim 1, wherein the material is present in a porous form. The method of claim 1, wherein the layer is deposited by electron-beam evaporation, sputtering, chemical vapor deposition, electrophoresis, slurry technology, sol-gel techniques or plasma spraying. The method of claim 1, wherein the layer has a sponge porous structure having a pore size of 50 to 900 μm. The method of claim 1, wherein the material is present in the form of an island-like, non-connected mass. 14. The method of claim 13, wherein the average size of each mass of material is less than 5 [mu] m. 14. The method of claim 13, wherein the mass of material is formed by use of a slurry, or deposition from a gaseous phase and further subsequent annealing. delete delete delete The method of claim 1, wherein the polymer matrix is highly cross-linked polyethylene. The composite material of claim 1, wherein the composite material is selected from the group consisting of Al ₂ O ₃ -MoO ₃ , ZrO ₂ -MoO ₃ , Al ₂ O ₃ -Mo-MoO ₃ , ZrO ₂ -Mo-MoO ₃ , TiO ₂ -MoO ₃ , TiO _{2 -Mo-MoO 3, SiO 2 -MoO} 3 or characterized in that the SiO ₂ -Mo-MoO _3. The method according to claim 20, wherein the content of MoO ₃ is 0.001 to 50 mole%, and the molar ratio of ZrO ₂ , Al ₂ O ₃ , TiO ₂ or SiO ₂ to MoO ₃ is 1 to 100. The method of claim 1, wherein the material is used as a component of a layer or layer for an implant. 23. The method of claim 22, wherein the implant is a catheter, a stent, a bone implant, a tooth implant, a vascular insert, or an endoprosthesis. 24. The method of claim 23, wherein the implant is a coronary artery stent made of Nitinol, which is coated with the material. 24. The catheter of claim 23, wherein the catheter is a port catheter comprising a chamber having a silicon membrane and a tube connected thereto, the chamber comprising at least a polymeric material or a polymeric material and / Characterized in that the polymeric material and / or the silicon film comprise a layer comprising a material and / or the polymeric material and / or the silicon film. The method of claim 1, wherein the material is used as a layer or layer component for absorbent sanitary articles or wound dressing, wherein the material is deposited or comprises a polymeric fiber or polymeric lattice comprising the material Lt; / RTI > The method of claim 1, wherein the material is used as a component of a layer or layer for a filter. The method of claim 1, wherein the material is used as a component of a layer or layer for a garment product comprising polymeric fibers on which the material is deposited or contain the substance. The method of claim 1, wherein the material is used as a component of a layer or layer for sanitary ware furnishings. Method according to claim 1, characterized in that the material is used as a component of a layer or layer for parts of switches, accessories, credit cards, keyboards, cell phone housings, coins, banknotes, door handles or parts of public transport equipment . delete The method of claim 1, wherein the material is used as a layer or a component of a layer in a nasal spray container. The method of claim 1, wherein the material is used as a layer or a component of a layer in a cable comprising polyurethane. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete